Regeneration of catalysts



Sept. 28, 1943.

u n L 4 0/1. l/VLET FnaM PREHEA T512 vjg C. E. HEMMINGER REGENERATION OF CATALYSTS Filed March 11, 1959 (EXHAUSTLINE I 60/1305 7706/ C'HA MBER.

GAS INLET Patented Sept. 28,1943

Charles E. Hemminger, Westfleld, N. J., 'assignor to Standard Oil Development Company, a

corporation oi Delaware Application March 11, 1939, Serial No. 261,174

11 Claims. The present invention relates to the novel features described hereinafter, reference being bad to the accompanying drawing, which shows one form oi' apparatus in which the invention may be practiced with good results.

In its broadest aspect, the invention relates to improvements in catalytic reactions. More particularly, the invention relates to the regeneration of a solid' orcontact catalyst-which has become contaminated or fouled during a catalytic reaction by a contaminant or poison which may be removed from the catalyst by oxidation and/or combustion.

In catalytic oil cracking employing a clay, zeolite. synthetic gel or some other solid catalytic catalyst, the cracking operation usually causes the deposition of a tarry carbonaceous deposit be periodically regenerated. The present invention proposes to regenerate such a catalyst by a combustion method'and to remove the gaseous products of combustion from the reactor. These gases contain together with CO2 and H20, appreciable quantities or CO, Ha, CH4 and other comon the catalystwhich impairs or destroys the efliciency of the catalyst so that the same must bustible. gases. These combustible gases result from incomplete combustion of the carbonaceous contaminants; alsoiro'm the water gas reaction,

from distillation of combustibles and the like.

I In the prior art practice, a portion of the gases resulting from the combustion of the catalyst contaminants is recycled to dilute the air or other oxygen-containing gas to absorb the heat 0! combustion in thereactor, so that the maximum temperature of combustion is limited. The combustibles in the recycle gas will, or course, burn when they contact the catalyst in conjunction with the air or oxygen and will be consumed and 0! no benefit in the regeneration.

This invention proposes to burn the combustlbies in the recycle gas in an external chamber 7 preferably in the presence of an oxidation propartially diagrammatically a vertical view or an apparatus selected to illustrate the invention.

In the drawing, the apparatus shown may be employed in the catalytic conversion 0! hydrocarbons. The usual preheating andrfractionating apparatus is not shown since the invention resides more' particularly in a method of preparing inert gas for dilution of oxygen or oxygen-containing gas during regeneration so that regeneration may be consummated more quickly without exceeding the maximum allowable temperature during the regeneration of spent catalyst, and hence, the drawing shows merely a suitable converter containing catalyst and such accessory apparatus as is necessary to carry out the novel features involved in the regeneration as hereinafter explained. That is to say. i and l-a represents. valved oxygen-containing gas inlet line to a reactor 2 of the vertical shell type containing a continuous bed of catalyst C; 3 represents an exhaust line through which the products of the combustion of' the catalyst contaminants or poisons are withdrawn; t represents a valved line leading to a combustion chamber 5 and line i-a connects chamber 5 and waste heat boiler 6. .Air inlet line 8 permits introduction of air into the gaseous products of combustion in line 4 or air may be introduced into the recycle gas through linev 20, but ordinarily the recycled gas passes I through 8 and into line I by way of line 20a. Inert gas from some outside source, viz. hot or cold carbon dioxide and/or superheated steam and/or nitrogen or mixture of these, or some equivalent gas, may be admitted through line 9. Surplus gas may be withdrawn from the system through line I0, and valve II in this line is controlled by a pressure regulator I 8 enabling the fixing or the gas back pressure in the system to some definite value. Pump fl causes circulation of gas during regeneration. In on-strearn operation, preheated oil is led into the reactor through line 12 and the reaction products are withdrawn through line l4.

In order to describe the present method of regeneration, it will be assumed that the catalyst C has become spent due to the accumulation of 1% to 5% by weight, of a carbonaceous con-- taminant iormed during an oil cracking operation. The temperature 01 the catalyst during crackingis ordinarily maintained at about 800 to 900 E, with a temperature or about 870 F. preierred, and at the end of the cracking phase is within this temperature range. The crackin operation is discontinued and then a thorough purging of the catalyst with superheated steam, nitrogen, carbon dioxide or mixtures thereof, or

through '3.

remaining after the cracking operation. After thorough purging, an oxygen-containing gas at a temperature of from about 600 F. to 800 F. is forced into reactor 2 from lines I and l-a by pump 7. The oxygen-containing gas admitted through line l-a contains from about 1% to about 10% oxygen as it enters reactor 2. Samples of gas may be taken from line l--a for analysis and based on this determination, the percent. of oxygen entering the reactor can be comtrolled. The contact of the oxygen-containing gas with the catalyst under the conditions here-. inafter specified in more detail causes an oxidation or a distillation of the catalyst contaminants and the gaseous products are withdrawn The. gases issuing from the-reactor 2 are at a temperature of about 950 F. to 1050 F. normally. These gases may contain as much as. 2% free hydrogen together with similar quantities of CO, hydrogen-carbon compounds and other combustible material. In'other words, the heated oxygen-containing gas which contacts the heated catalyst C and is forced therethrough does not ordinarily convert all of the combustible con-.

taminants or catalyst poisons to non-combustible material but rather, as stated, the efliuent gases passing out of the reactor through line 3 contain appreciable quantities of combustible materiaL' These gases are passed into line 4 and air or some gas containing free oxygen is admitted through line Q to line 4. The amount of air here admitted is the total-required for burning of combustibles in line 4 in the combustion chamber 5 and for subsequent regeneration in reactor 2. The comhustibles and the air or the like are then led to chamber 5, and burned. The combustion causes an increase of the temperature to about 1200 F. or higher and sensible heat may be recovered from this latter combustion process by heat transfer in waste heat boiler 6 until the temperature of the gases is reduced to from about 700 F. to 800 F. or thereabouts. The combustion products of 5 are therefore passed through waste heat boiler 5 to recover this heat and to cool the gases. From wasteheat boiler 6 the gases pass through line 20-a to line I. A portion of the cooled gas thus produced may be withdrawn through line It) and the remainder recirculated.

At the beginning of the regeneration phase, it may be necessary in order to start the regeneration process, i. e., to cause ignition of the'combustible contaminants on catalyst C, to introduce a hot inert gas, say at a temperature of 650 to 800 F. through lines 25, 4; 20, i and I'a into reactor 2, a small amount of air being added to. the inert gas through inlet 8 or 8a. If desired, a further quantity of some inert diluent gas either hot or cold, suchas nitrogen, steam, carbon dioxide or the like, or mixtures of such gases, may be admitted through line 9.

The entering regeneration gas is preferably under a gauge pressure of 5 to 125 lbs. per squareinch with about 45 lbs. per quare inch preferred. The pressure within the reactor is indicated by hot products of combustion in advance of the somesuitable gauge [1 or the like and may be regulated by means of mechanism It operating valve H- in line I0.

The combustion will commencein the mcdiflcation shown at some level or zone near the bottom of the reactor 2 and will proceed upwardly as the regeneration proceeds. The progress of the regeneration can be followed by observation of the temperatures prevailing at various levels as indicated by the thermocouples IE or the like. In an elongated bed of catalyst, due to the flow of us say in the neighborhood of B in the drawing has been preheated by combustion products from lower zones or regions to temperature of 900 F.

to 1000 F. or thereabouts, the oxygen concentration in the incoming gas should be lowered considerably at once, say to 0.5% concentration or thereabouts and/or the temperature of the recycled gas should be lowered to about 500 F. or

lower-by introducing cold inert gas through line 9.

The recycled gas, or the gas which flows out through exhaust line 3 in normal operation, in say a 100 barrel 9. day unit may have an analysis about as follows:

Per cent CO2 8a C0 2.6

Hz 0.2 O: 8.8 N 80.0

If the carbon monoxide and hydrogen in 100 cu. ft. of the above gas were burned, 900B. t. u.s of heat would be released per 200 cu. it. under standard conditions, of the outlet gas to-be recycled. As nearly of this available heat was evolved in the combustion chamber 5, the temperature of the'efiluent gas would be increased about 340 F. With an inlet gas temperature of 750 F. and an outlet gas temperature of 950 F., both with respect to the reactor, the inlet gas temperature to the waste heat boiler would be about 1290 F. rather than 950 F. according to the known processes. It is, therefore, obvious that-the carbon can be removed from the reactor fasterand with less recirculation of gases with an overall temperature difference of 540 F. This greater temperature difference is due to the re-. moval of some of the carbon as CO rather than CO2 because of the reaction of CO: with carbon on the catalyst.

It is believed obvious that the present invention is adapted to regeneration not only of oil cracking catalysts but of any solid catalyst contaminated with combustible material and that the catalyst may be regenerated in situ or outside the reactor.- In the former case by appropriate pipe connections. and manifolding, it is possible to regenerate a catalyst not only in a reactor of the type shown, but also when the catalyst is con tained in tubes, supported on trays or when the modifications falling within the scope of the appended claims.

' gen to the reaction chamber.

I claim:

1. In the regeneration of an adsorbent catalyst" by the combustion of contaminating material deposited thereon during a catalytic reaction, the improvement which comprises substantially completely removing combustible material from the effluent regeneration gases by burning said gases I of a contaminating deposit, the i movement which comprises forcing a gas cont ining from 1% to free oxygen through the catalyst in the reaction zone atcombusti'on temperatures,

withdrawing the products of the combustion from the reaction zone and conducting them to a combustion chamber and therein substantially completely removing the combustibles contained in said withdrawn gases by burning in the presence of an oxidation promoter, withdrawing the gases from the combustion chamber, reducing the temperature of the withdrawn gases by passing the gases through aw'aste heat boiler wherein the prises forcing a heated oxygen containing gas through said catalyst causing combustion of catalyst contaminants, withdrawing the products of ing the cooled gases to the catalyst undergoing regeneration.

7. The process of regenerating a contaminated catalyst which comprises maintaining a catalyst zone and acombustion zone separated therefrom, forcing an oxygen'containing gas throughthe catalyst under conditions causing combustion of the contaminants, removingthe gaseous products of combustion containing combustibles from the catalyst zone, passing the last-named gases together with added oxygen containing gas to said combustion zone, and causing substantially complete combustion of the combustibles in said last-named gases and returning the products of the last-named combustion containing substantially no combustible material to the catalyst undergoing regeneration. 7

8. The process as set forth in claim 'Iin which the amount of oxygen added to the gases issuing from the catalyst'zone is in excess of that required to cause combustion of all of the combustibles in said gases.

combustion containing combustibles from the catalyst, adding an oxygen containing gas there-' to, substantially'burning the combustibles and returning the last-named gas to the catalyst undergoing regeneration r 5. In the process of regenerating a catalyst containing contaminants by combustion ohsaid gases to the catalyst undergoing regeneration. 8. In the process of'regenerating a catalyst containing contaminants by combustion of said contaminants, the improvement comprising removing from the catalyst zone, the gaseous products resulting from a combustion of the catalyst contaminants which gaseous products contain combustibles, adding .an oxygen containing cause combustion of the said combustibles, causin: combustion of the combustibles in the presence of e heavymetal oxide promoter, removing a portion of the heatfrom the gases and return- 9, The process of regenerating a contaminated catalyst which comprises forcing an oxygen containing gas at a temperature of from about 750 F. through said catalyst which is at a temperature of between about 800 to 900 F., withdrawing the resulting gases, said gases having a temperatureoi about 950 F., adding excess oxygen containing gas and burning the combustibles in the said-gases causing a temperature rise to about 1290 F., recovering heat from the gases resulting from the said burning in an amount such that the temperature thereof is reduced to about 750 F. and returning the gases at this temperature to the reactor for continuation of the regeneration.

10. The process of regenerating a solid catalyst contaminated with a tarry deposit which comprises forcing a heated oxygen containing gas through said catalyst causing combustion of catalyst contaminants, withdrawing the products of combustion containing combustibles from the tion zone at temperatures sumciently high to gas containing more oxygen than necessary to catalyst, adding an oxygen containing gas thereto, substantially burning the combustibles and returning. the last-named gas to the catalyst undergoing regeneration.

11. The process of regenerating a solid catalyst contaminated with V-carbonaceous deposits which comprises forcing a heated oxygen-containing gas through said catalyst in a regeneracause combustion ofthe catalyst contaminants,

withdrawing the gaseous products of combustion containing combustibles from the regeneration zone, adding an oxygen-containing gas to said gaseous products of combustion from ,the combustion zone to the catalyst in the'regeneration zone, together with oxygen-containing gas. 

